CN104497346A - Super-hydrophobic high-oil-absorbing melamine-resin sponge and preparation method thereof - Google Patents
Super-hydrophobic high-oil-absorbing melamine-resin sponge and preparation method thereof Download PDFInfo
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- CN104497346A CN104497346A CN201410668027.8A CN201410668027A CN104497346A CN 104497346 A CN104497346 A CN 104497346A CN 201410668027 A CN201410668027 A CN 201410668027A CN 104497346 A CN104497346 A CN 104497346A
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Abstract
The invention relates to a super-hydrophobic high-oil-absorbing melamine-resin sponge and a preparation method thereof. The chemical structure of the skeletal structure surface of the melamine-resin sponge is as described in the specification, wherein R is an aliphatic alkyl group, a phenyl group or a methylphenyl group. The super-hydrophobic high-oil-absorbing melamine-resin sponge provided by the invention has high porosity, super hydrophobicity, high oil-absorption rate and good mechanical strength, and can be applied as a repeatedly-usable absorbent for oil spill on water in the industry of cleaning of oil spill on water surfaces of rivers, lakes and seas.
Description
Technical field
The present invention relates to polymeric material field, particularly relate to a kind of melmac sponge and preparation method thereof.
Background technology
Melmac sponge is a kind of high porosity wetting ability hole-opening foaming macromolecular material, has good elasticity and thermotolerance, is widely used in sound isolating and flame-retardant finishing material.This hydrop iotaiilic sponge is owing to having the porosity of more than 99% and a hundred or so micron-sized aperture structure, and this structure has excellent water suction and the effect of control water, can reach the water-intake rate of about 100 times.Owing to forming the hydrophilic interaction of the chemical structure of this material, make its to swim in slick without any adsorption, to the oily waste treatment engineering in sea, river, rivers and lakes without any help and contribution.
Summary of the invention
The object of the present invention is to provide a kind of melmac sponge of super-hydrophobic, high oil suction.
Another object of the present invention is to the preparation method that a kind of above-mentioned melmac sponge is provided.
Super-hydrophobic high oil suction melmac sponge of the present invention, the chemical structure on its skeleton structure surface is:
Wherein, R is aliphatic alkyl or phenyl or aminomethyl phenyl.
Preferably, described aliphatic alkyl is-CH
3,-CH
2cH
3,-CH
2(CH
2)
mcH
3,-CH
2cH (CH
3) CH
3,-CH
2(CH
2)
qcH (CH
3) CH
3; Wherein, m=1,2,3,4 ... 16; Q=1,2,3,4 ... 14.
Super-hydrophobic high oil suction melmac sponge of the present invention is by by melmac sponge impregnating gained in the aprotic solvent of alkyl or phenyl or aminomethyl phenyl trichlorosilane.Reactions change process is shown below:
Preferably, in above formula, R is-CH
3,-CH
2cH
3,-CH
2(CH
2)
mcH
3,-CH
2cH (CH
3) CH
3,-CH
2(CH
2)
qcH (CH
3) CH
3, phenyl or aminomethyl phenyl; Wherein, m=1,2,3,4 ... 16; Q=1,2,3,4 ... 14.
This super-hydrophobic high oil suction melmac sponge is reacted in aprotic solvent dipping solution by the melmac molecule on the fibrous skeleton material surface in melmac sponge and alkyl or phenyl or aminomethyl phenyl trichlorosilane, form hydrophobic alkyl or phenyl or methylphenyl siloxane chemical structure, make hydrophilic melmac sponge generation performance reversion, be modified as the melmac sponge three-dimensional net structure of super-hydrophobic high oil suction.
Super-hydrophobic high oil suction melmac cavernous body of the present invention is high porosity three-dimensional crosslinked network structure, porosity is at 98.5-99.5%, do not infiltrated completely in water, the contact angle of cavernous body surface and water droplet is between 130-160 °, to apolar substance, as oils has wetting property and the absorptivity of height, every gram of cavernous body oil number is between 95-110 gram, and the melmac sponge of this surface modification has good mechanical property, " oil suction/extruding " repetitive operation of 500-1000 time can be experienced.The manufacture craft with the melmac sponge of the alkylsiloxane surface modification of this characteristic is easy, is applicable to scale operation preparation, will be widely used in the cleaning industry of rivers,lakes and seas water surface oil slick pollution.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to technique means of the present invention can be better understood, and can be implemented according to the content of specification sheets, and can become apparent to allow above and other object of the present invention, feature and advantage, below especially exemplified by preferred embodiment, be described in detail as follows.
Embodiment
For further setting forth the present invention for the technique means reaching predetermined goal of the invention and take and effect, below in conjunction with preferred embodiment, to the super-hydrophobic high oil suction melmac sponge proposed according to the present invention and preparation method thereof its embodiment, structure, preparation method, step, feature and effect thereof, be described in detail as follows.
Embodiment 1: the preparation of the melmac sponge of METHYL TRICHLORO SILANE modification
(1) melmac cavernous body skeleton surface hydration process: German BASF melmac sponge (white; Density: 6.8mg/cm
3) one piece, volume is 3.0 × 3.0 × 5.0=45.0cm
3, drying 2 hours in 100 DEG C of baking ovens, weigh 306mg.Then be placed on 32 DEG C, humidity is in the encloses container of 90% 1 hour, and taking-up is weighed, 318.24mg (its water absorbent surface 12.24mg accounts for 4.0% of sponge skeleton weight).
(2) melmac cavernous body skeleton surface modification treatment: take 99.50g toluene and add in the small beaker of 250ml, take 0.50g METHYL TRICHLORO SILANE again and be dissolved in above-mentioned toluene the METHYL TRICHLORO SILANE toluene solution forming 0.5%, and the melmac sponge impregnating in above-mentioned toluene solution 30 minutes having done water absorbent surface process in (1) will be tested.Extrude toluene solution contained by cavernous body after taking-up, then forced air drying 2 hours in 80 DEG C of convection oven, collects super-hydrophobic high oil suction melmac sponge.Cavernous body is weighed 307.5mg, weightening finish 0.49%.
(3) performance characterization: the density of super-hydrophobic high oil suction cavernous body is 6.85mg/cm
3, porosity is: 99.56%; Mean pore size 118 μm; Tensile strength is 120KPa, elongation at break is 122%; Air permenbility under 8.4Pa (0.08bar) pressure is 3000Lm
-2s
-1; The contact angle of water droplet and this cavernous body is 132 °.This super-hydrophobic high oil suction cavernous body all has very high sorption to the toluene swum on the water surface, sherwood oil, edible oil, diesel oil, machine oil, gasoline etc., for diesel oil: every cubic centimetre of modified sponge body absorbs diesel oil 0.6508g, be equivalent to every gram of modified sponge body and absorb 95g diesel oil.The diesel oil amount of the 500th oil suction/extrude is 0.6425g, namely still maintains the oil suction efficiency of 99%.Embodiment 2: the preparation of the melmac sponge of octadecyl trichlorosilane alkane modification
(1) melmac cavernous body skeleton surface hydration process: German BASF melmac sponge (white; Density: 6.8mg/cm
3) one piece, volume is 3.0 × 3.0 × 5.0=45.0cm
3, drying 2 hours in 100 DEG C of baking ovens, weigh 306mg.Then be placed on 32 DEG C, humidity is in the encloses container of 90% 1 hour, and taking-up is weighed, 316.71mg (its water absorbent surface 10.71mg accounts for 3.5% of sponge skeleton weight).
(2) melmac cavernous body skeleton surface modification treatment: take 99.50g sherwood oil and add in the small beaker of 250ml, take 0.50g octadecyl trichlorosilane alkane again and be dissolved in above-mentioned sherwood oil the octadecyl trichlorosilane alkane petroleum ether solution forming 0.5%, and the melmac sponge impregnating in above-mentioned toluene solution 25 minutes having done water absorbent surface process in (1) will be tested.Extrude petroleum ether solution contained by cavernous body after taking-up, then forced air drying 2 hours in 80 DEG C of convection oven, collects super-hydrophobic high oil suction melmac sponge.Cavernous body is weighed 309.0mg, weightening finish 0.98%.
(3) performance characterization: the density of super-hydrophobic high oil suction cavernous body is 6.87mg/cm
3, porosity is: 99.56%; Mean pore size 118 μm; Tensile strength is 123KPa, elongation at break is 125%; Air permenbility under 8.4Pa (0.08bar) pressure is 2000Lm
-2s
-1; The contact angle of water droplet and this cavernous body is 160 °.This super-hydrophobic high oil suction cavernous body all has very high sorption to the toluene swum on the water surface, sherwood oil, edible oil, diesel oil, machine oil, gasoline etc., for machine oil: every cubic centimetre of modified sponge body absorbs machine oil 0.7557g, be equivalent to every gram of modified sponge body and absorb 110.0g machine oil.The oil level of the 1000th oil suction/extrude is 0.7179g, namely still maintains the oil suction efficiency of 95%.
Embodiment 3: the preparation of the melmac sponge of phenyl-trichloro-silicane modification
(1) melmac cavernous body skeleton surface hydration process: German BASF melmac sponge (white; Density: 6.8mg/cm
3) one piece, volume is 3.0 × 3.0 × 5.0=45.0cm
3, drying 2 hours in 100 DEG C of baking ovens, weigh 306mg.Then be placed on 32 DEG C, humidity is in the encloses container of 90% 1 hour, and taking-up is weighed, 316.71mg (its water absorbent surface 10.71mg accounts for 3.5% of sponge skeleton weight).
(2) melmac cavernous body skeleton surface modification treatment: take 99.50g tetrahydrofuran (THF) and add in the small beaker of 250ml, take 0.50g phenyl-trichloro-silicane again and be dissolved in above-mentioned tetrahydrofuran solvent the phenyl-trichloro-silicane tetrahydrofuran solution forming 0.5%, and the melmac sponge impregnating in above-mentioned tetrahydrofuran solution 35 minutes having done water absorbent surface process in (1) will be tested.Extrude tetrahydrofuran solution contained by cavernous body after taking-up, then forced air drying 2 hours in 80 DEG C of convection oven, collects super-hydrophobic high oil suction melmac sponge.Cavernous body is weighed 308.1mg, weightening finish 0.69%.
(3) performance characterization: the density of super-hydrophobic high oil suction cavernous body is 6.85mg/cm
3, porosity is: 99.56%; Mean pore size 120 μm; Tensile strength is 120KPa, elongation at break is 121%; Air permenbility under 8.4Pa (0.08bar) pressure is 2800Lm
-2s
-1; The contact angle of water droplet and this cavernous body is 142 °.This super-hydrophobic high oil suction cavernous body all has very high sorption to the toluene swum on the water surface, sherwood oil, edible oil, diesel oil, machine oil, gasoline etc., for edible oil: every cubic centimetre of modified sponge body absorbs edible oil 0.7303g, be equivalent to every gram of modified sponge body and absorb 106.6g edible oil.The quantity of edible oil of the 750th oil suction/extrude is 0.7085g, namely still maintains the oil suction efficiency of 97%.
Above experiment material and result test:
(1) experiment material:
A kind of melmac sponge, three kinds of alkyl or phenyl trichlorosilanes and three kinds of alkanes or the low polar solvent without reactive hydrogen is employed in 3 embodiments of the present invention.All solvents or reagent are all bought by commercial channel.
(2) experimental result testing and characterization
In the present invention, the experimental result of 3 embodiments is tested routinely by following plant and instrument and characterizes.
1) aperture size of melmac sponge and super-hydrophobic high oil suction melmac sponge measures with scanning electronic microscope VEGA3SBU (Czech Republic);
2) mechanical properties (intensity, extension at break etc.) of super-hydrophobic high oil suction melmac sponge measures with the miniature control electronic universal tester of CMT8102 (Shenzhen SANS material tests company limited);
3) porosity of melmac sponge and super-hydrophobic high oil suction melmac sponge is calculated by following formula:
Porosity β=[1-(ρ/ρ
o)] × 100
Wherein ρ be melmac sponge or super-hydrophobic high oil suction melmac sponge density (gram/cm
3), ρ
ofor the density (1.57g/cm of corresponding melmac solid film
3);
4) contact angle of super-hydrophobic high oil suction melmac sponge and water measures with CA100A type contact angle measurement (Shanghai Ying Nuo precision instrument company limited); The permeability of super-hydrophobic high oil suction melmac sponge measures with Full-automatic gas transmitance instrument Porometer3GZH (Kang Ta instrument company of the U.S.).
The above, it is only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention, any those skilled in the art, do not departing within the scope of technical solution of the present invention, make a little change when the technology contents of above-mentioned announcement can be utilized or be modified to the Equivalent embodiments of equivalent variations, in every case be the content not departing from technical solution of the present invention, according to any simple modification that technical spirit of the present invention is done above embodiment, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (10)
1. a super-hydrophobic high oil suction melmac sponge, is characterized in that the chemical structure on the skeleton structure surface of described melmac sponge is:
Wherein, R is aliphatic alkyl or phenyl or aminomethyl phenyl.
2. super-hydrophobic high oil suction melmac sponge as claimed in claim 1, is characterized in that described aliphatic alkyl is-CH
3,-CH
2cH
3,-CH
2(CH
2)
mcH
3,-CH
2cH (CH
3) CH
3,-CH
2(CH
2)
qcH (CH
3) CH
3;
Wherein, m=1,2,3,4 ... 16; Q=1,2,3,4 ... 14.
3. super-hydrophobic high oil suction melmac sponge as claimed in claim 1 or 2, is characterized in that the contact angle of water droplet on this super-hydrophobic sponge is between 130-160 °.
4. super-hydrophobic high oil suction melmac sponge as claimed in claim 1 or 2, is characterized in that the porosity of described melmac sponge is between 98.5-99.5%.
5. super-hydrophobic high oil suction melmac sponge as claimed in claim 1 or 2, is characterized in that the Air permenbility of described melmac sponge under 12.6Pa pressure is at 2000-3000Lm
-2s
-1between.
6. a preparation method for super-hydrophobic high oil suction melmac sponge, is characterized in that it is by by melmac sponge impregnating gained in the aprotic solvent of alkyl or phenyl or aminomethyl phenyl trichlorosilane.
7. the preparation method of super-hydrophobic high oil suction melmac sponge as claimed in claim 6, is characterized in that described alkyl is-CH
3,-CH
2cH
3,-CH
2(CH
2)
mcH
3,-CH
2cH (CH
3) CH
3,-CH
2(CH
2)
qcH (CH
3) CH
3;
Wherein, m=1,2,3,4 ... 16; Q=1,2,3,4 ... 14.
8. the preparation method of super-hydrophobic high oil suction melmac sponge as claimed in claims 6 or 7, is characterized in that described aprotic solvent is one or more mixing in following solvent: hexanaphthene, normal hexane, sherwood oil, methylene dichloride, tetrahydrofuran (THF), toluene, pentanone-2, cyclopentanone, o-Xylol, pimelinketone.
9. the preparation method of the super-hydrophobic high oil suction melmac sponge as described in any one of claim 6-8, is characterized in that described melmac sponge carries out Skeleton Table face hydration process before dipping, makes its surface moisture account for the 3.5-4% of sponge skeleton weight.
10. the preparation method of the super-hydrophobic high oil suction melmac sponge as described in any one of claim 6-9, after it is characterized in that having flooded, extrudes solution contained by cavernous body and carries out drying to sponge.
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| CN104888497A (en) * | 2015-05-28 | 2015-09-09 | 南京理工大学 | Super-hydrophobic and super-oleophylic fluorocarbon resin block and preparation method thereof |
| CN104987528A (en) * | 2015-06-29 | 2015-10-21 | 武汉工程大学 | Modification method of oleophylic and hydrophobic nano-sponge |
| CN105148565A (en) * | 2015-10-23 | 2015-12-16 | 重庆工商大学 | Method for ultrasonic-assisted demulsification and dehydration of super-oleophilicity/super-hydrophobic materials |
| CN105801903A (en) * | 2016-03-17 | 2016-07-27 | 中国船舶重工集团公司第七二五研究所 | Preparation method and corrosion-preventing implementation method of super-hydrophobic sponge material |
| CN106215904A (en) * | 2016-09-27 | 2016-12-14 | 郑州峰泰纳米材料有限公司 | A kind of method obtaining oil absorption material for substrate with melamine resin foam |
| CN107011534A (en) * | 2017-03-14 | 2017-08-04 | 华南理工大学 | A kind of super-hydrophobic super-oleophylic melamine foamed plastic and preparation method and application |
| CN109206658A (en) * | 2017-07-07 | 2019-01-15 | 天津大学 | A kind of preparation method of super-hydrophobic blown rubber |
| CN112832216A (en) * | 2020-12-31 | 2021-05-25 | 郑州峰泰纳米材料有限公司 | Oil-absorbing water delivery device for offshore oil |
| US11214646B2 (en) | 2018-02-16 | 2022-01-04 | South Dakota Board Of Regents | Highly hydrophobic and oleophilic melamine resin via metal-ion induced wettability transition, application, and preparation thereof |
| CN114292435A (en) * | 2022-02-18 | 2022-04-08 | 天津德高化成新材料股份有限公司 | Preparation method of mold moistening sponge for semiconductor packaging mold |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104888497A (en) * | 2015-05-28 | 2015-09-09 | 南京理工大学 | Super-hydrophobic and super-oleophylic fluorocarbon resin block and preparation method thereof |
| CN104888497B (en) * | 2015-05-28 | 2016-07-06 | 南京理工大学 | Super-hydrophobic and super-oleophylic fluorocarbon resin block and preparation method thereof |
| CN104987528A (en) * | 2015-06-29 | 2015-10-21 | 武汉工程大学 | Modification method of oleophylic and hydrophobic nano-sponge |
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| CN105801903B (en) * | 2016-03-17 | 2019-01-15 | 中国船舶重工集团公司第七二五研究所 | A kind of preparation and its anticorrosion implementation method of super-hydrophobic sponge material |
| CN106215904A (en) * | 2016-09-27 | 2016-12-14 | 郑州峰泰纳米材料有限公司 | A kind of method obtaining oil absorption material for substrate with melamine resin foam |
| CN107011534A (en) * | 2017-03-14 | 2017-08-04 | 华南理工大学 | A kind of super-hydrophobic super-oleophylic melamine foamed plastic and preparation method and application |
| CN109206658A (en) * | 2017-07-07 | 2019-01-15 | 天津大学 | A kind of preparation method of super-hydrophobic blown rubber |
| US11214646B2 (en) | 2018-02-16 | 2022-01-04 | South Dakota Board Of Regents | Highly hydrophobic and oleophilic melamine resin via metal-ion induced wettability transition, application, and preparation thereof |
| CN112832216A (en) * | 2020-12-31 | 2021-05-25 | 郑州峰泰纳米材料有限公司 | Oil-absorbing water delivery device for offshore oil |
| CN114292435A (en) * | 2022-02-18 | 2022-04-08 | 天津德高化成新材料股份有限公司 | Preparation method of mold moistening sponge for semiconductor packaging mold |
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Application publication date: 20150408 |